Method of destroying fungi with nitrophenyl sulfonylethylene



United States Patent M Int. Cl. A0111 9/14 US. Cl. 424337 ClaimsABSTRACT OF THE DISCLOSURE The invention describes the use of compoundsof the formula in which X is selected from the group consisting of H, Cland N0 for destroying fungi and spores.

The present invention is a division of copending application Ser. No.261,819, filed Feb. 28, 1963, now Patent No. 3,358,035, and relates tothe fungicidal use of a new class of ethyl sulfonic compounds whichexhibit both anticryptogamic activity and a low toxicity towardswarmblooded animals.

The compounds of the invention have the formula NO: X

in which X is selected from the group consisting of hydrogen, chlorineand NO group, and Y is a halogen atom. I have found that compoundshaving the above formula are active against fungi and spores withoutimpairing at the same time the parts of the plant with which they arecontacted.

Among the compounds having the above formula 1-chloro-2-p-nitropheny1-sulfonyl-ethylene is particularly active. Otherpreferred compounds are1-chloro-2-(2,4-dinitrophenyl-sulfonyl)-ethylene, 1-chloro-2-(3 nitro 4-chlorophenyl-sulfonyl)-ethylene, 1-chloro-2 (3 nitrophenyl-sulfonyl)-ethylene.

The compounds of the invention can be used in the conventional form ofaqueous emulsions 0r suspensions or powders. The emulsions are preparedby known methods, by dissolving the active substances in suitablesolvents in the presence of emulsifiers. Wettable powders (employablefor suspensions in Water) are obtained by grinding the active substancesuntil the required fineness is reached, adding inert fillers such askaolin, talc and bentonite and a suitable dispersing agent. Dustingpowders are prepared by grinding the active substances with the additionof inert fillers of the aforementioned type.

In the compositions provided by the present invention, in addition tothese auxiliary substances, there can be used also other substanceshaving pesticidal or other activity.

Patented Apr. 1, 1969 One type of liquid formulation can be prepared bymixing the active substance with a suitable solvent, e.g. dioxane, anon-ionic surface active agent such as the condensation products ofethylene oxide with an alkyl phenol, and an anionic surface-active agentsuch as an alkylarylsulfonate or an alkylsulfate.

The fungicidal activity of the compounds having the Formula 1 is in somecases particularly high. Thus, for instance,1-chloro-2-p-nitrophenyl-sulf0nyl-ethylene presents an activity againstdownygrape mildew (Plasmopara vitfcola) about twice, and against thespores of Alternaria ten'wis more than four times that of zinc ethylenebisdithiocarbamate (Zineb), which is one of the best knownanticryptogamic compounds.

A very favorable characteristic of the compounds of the invention istheir low toxicity towards warm-blooded animals. For instance, 1000mmg./kg. of 1-chloro-2- p-nitrophenyl-sufonyl-ethylene give a mortalityof 0% per os on mice; 200 mmg./ kg. of1-chloro-2-p-nitrophenylsulfonyl-ethylene give a mortality of 0% byintravenous application on mice.

The compounds of my invention can be prepared by conventional methods(see Gazzetta Chimica Italiana, 86, 1956, page 413). Thus, for example,l-chloro-Z-p-nitrophenyl-sulfonyl-ethylene is obtainable froml-chloro-Z- p-nitrophenyl-mercaptoethylene by oxidation with hydrogenperoxide in the presence of glacial acetic acid as follows:

Into a 1-liter flask provided with an agitator, thermometer, refluxcondenser and dropping funnel, are introduced g. of1-chloro-2-p-nitrophenyl-mercaptoethylene and 170 cc. of glacial aceticacid. The reaction mixture is heated to -75 C., until completedissolution. While agitating, a mixture of:

Co. Hydrogen peroxide (30-33%) Glacial acetic acid 175 Concentratedsulfuric acid 5 is introduced within 20 minutes. During the introductionof the latter substances, the temperature of the reaction mixture risesup to 100 C. At the end of the addition, the mixture is left to cool.The reaction product is separated in a bulky crystalline form aftercooling to 10 C., filtrating and washing with water to neutrality. 64 g.of a straw-yellow product having a melting point of 157 C. are obtained.The analysis shows:

S calculated: 12.95

S found: 12.88-12.9470.

The product obtained is soluble in acetone, benzene, dioxane anddimethylacetamide, is scarcely soluble in ethanol and is insoluble in HO.

1-chloro-2-(2,4-dinitrophenylsulfonyl)-ethylene can be prepared by themethod described in J.A.C.S., 77, page 3390.

1-chloro-2-(3-nitr0-4-chlorophenyl-sulfonyl) ethylene is obtainable bynitration of 4-chl0ro-phenylsulfonyl-2- chloroethylene.

The following examples are given to illustrate the activity of some ofthe compounds of the invention and also the method of preparing them,without limiting the scope of the invention.

EXAMPLE 1 10 parts by weight of 1-chloro-p-nitrophenyl-sulfonylethyleneare introduced into a mixer, together with 83 parts by weight ofdioxane, 4 parts by weight of a nonionic surface active agent,consisting of the condensation product of ethylene oxide with an alkylphenol, and 3 parts by weight of an anionic surface active agent,consisting of calcium dodecylbenzene sulfonate. The mixture is agitatedat room temperature until it becomes homogeneous. A water-emulsifiablesolution is thus obtained.

EXAMPLE 2 23.7 g. of 4-chloro-phenyl-sulfonyl-2-chloroethylene aredissolved in 51 cc. of concentrated H 50 While vigorously agitating at-10 C., a mixture consisting of 7.5 g. of 98.5% --HNO (fuming) and g. ofconcentrated H 80 is added dropwise within 5 minutes, At the end of theaddition, the whole is further agitated at 5l0 C. for 10 minutes and isthen heated to about C. and left to stand for one hour. The mixture isthen poured into 700 g. of an ice-water mixture, and the product isfiltered and washed with water to neutrality. 31.5 g. of1-chloro-2-(3-nitro-4-chlorophenylsulfonyl)- 4 EXAMPLE 4 (A) Cupmethod.-Three porcelain cups, fish spine beads, each containing 0.025cc. of a solution with a known content of the product to be examined,are placed on the surface of Petri dishes with a diameter of 10 cm.,which were previously coated with agar-agar seeded with the four testfungi. After incubation in a thermostat at 25 C. for 72 hours, theinhibition halos of fungi growth on the agar-gar surface (distance inmm. between the outer edge of the cup and the point where the testfungus begins to grow) are determined.

The results of the evaluations of the products under examination(expressed in mm.) are reported in the following table:

a.s. Inhibition haloes (millimeters) Products conc.,

percent Alterrmria Aspcrgillus Pmlcillium Saccaromyces tenure N. niger TRoguejorli T ellipsoideus [-1 Sodium pentachlorophenate (Santobrite) 123 21 21 11 0.2 17 11 14 4 0. 04 9 6 7 41-ch10ro-2-p'nitro-phenyl-sulfonyl-ethylene 1 28 14 15 12 0. 2 24 12 1410 0. 04 15 6 7 0 1-ch1oro-2-(2,4-dinitrophenylsulfonyl)ethylene 1 28 1318 11 l-chlor0-2-(3-nitro-4chl0rophenyl-sulfony1)-ethylene 1 32 12 16 111-ch1oro-2-(3-nitropheny1su1fony1)ethylene 1 29 16 22 11 ethylene(colorless amorphous solid) having a melting point of l06-109 C. areobtained. A sample crystallized from methanol has a melting point of1091l0 C.

C1 calculated=25.l3%; Cl found=25.25-25.27%. N calculated=4.96%; Nfound=5.12%.

EXAMPLE 3 (B) Streak method.-The solution of the product is incorporatedin the nutritive medium while the inoculation of the test fungi iscarried out by means of streaks with spore suspension.

The reading of the plates if made after 72 hours by evaluating thegrowth of the fungi according to the following scale:

0=No difference compared with the control water. 1=Slight differencecompared with the control water. 2=Colonies spread in all the streak.

3=Some colonies in only one point of the streak. 4=No fungi growth.

The results are reported in the following table:

as Inhibition haloes (millimeters) Products conc.,

percent AZter /mrz'a Aspergillus Penicillium Saccaromycea temtts N.'mger T Roqueforti T ellipsoz'deus H Sodium pentachlorophenate(Santobrite) 0.02 4 4 4 1 ch1oro-2-p-nitropheny1sulfonylethylene 0.02 44 4 4 0.004 4 4 3 2 0. 0008 4 3 2 11-eh1oro-2-(2,4-dinitropheny1sulionyl)-ethylene 0.02 4 3 3 01-chl0ro-2-(3-nitro-4-chlorophenylsulfouyl)-ethylene 0.02 4 4 4 41-ch1oro-2-(3-nitrophenylsuliony1)-ethylene 0. 02 4 4 4 4 thermostat at25 C. for 72 hours, the inhibition haloes EXAMPLE 5 of fungi growtharound these discs are determined by measuring on the agar-agar surfacethe distance (expressed in mm.) between the disc edge and the point atTests on spores of Alternaria tenuis (slidegermination method) which thetest fungus begins to grow. Suspension of product prepared with doses ingeomet- The results obtained are reported in the following IicalProgression (ratio and With added spores of table. Alternaria tenuistaken from 3-day old cultures are placed as. Inhibition haloes(millimeters) Products cone,

percent AZtemaria Aspergillus Penicillium Saccaromyces tenm's N. 'm'gerT Rogue/011i T ellipsoideus H Sodium pentachlorophenate (Santobrite) 121 18 19 9 0. 2 11 7 11 4 0. 04 4 4 4 21-chloro-2-p-nitrophenyl-sulionylethylene 1 18 4 6 2 0. 2 16 3 5 2 0. 0415 3 4 1 l-chloro-Z-(2,4-dinitrophanylsulionyl)-ethylene 1 20 6 l2 51-cl1loro-2-(3-nitr0-4-chlorophenylsulionyl)-ethylene 1 23 3 6 21-chlor0-2-(3-nitrophenylsullonyl) ethylene 1 as drops on slides. Afterabout hours, the inhibition of the spore germination is determined byreading on the microscope.

In the following table is reported the average of three repetitions foreach dose.

The leaves, placed with the lower page turned upwards, are treated withaqueous suspensions of the product to be examined and, when the depositis dried, are infected with Botrytis conidia. After 6 days the resultsare read by 5 counting the infection spots on each leaf.

Percentage of germinated spores, corrected on the basis of mortalitypfthe control water and of the length of the tube of the germinated spores(average capacity of germination of untreated controls: 97%) Test dosea.s., percent Zinc ethylene- 1-chloro-2-p-nitro- 1-chloro-2-(2,4-1-chloro-2-(3-nitro- 1-oh1oro-2-(3- bisdithiocarbamatephenyl-sulfonyldinitro-phenyl-sul- 4-chlorophenyl-su1-nitrophenyl-sulethylene ionyl)-ethylene ionyl)-ethylene fonyD-ethyleneEXAMPLE 6 Tests on Uromyces appendiculatus (bean rust) Percent infectioncompared with that of the untreated control (average infection ofuntreated controls: about 900 pustules per leaf) Zine ethylene-bis-di-Test dose, percent of as.

1-chloro-2-p-nitrothlocarbamate phenyl-sulfonylethylene EXAMPLE 7Activity test on downygrape mildew (Plasmopara viticola) Vine leavesgrown in pots under artificial light are removed and preserved on thebottom of Petri dishes, adapted to act as wet rooms by means of a filterpaper sheet kept wet by a small piece of synthetic sponge im pregnatedwith water. The leaves, placed with the lower page turned upwards, aretreated with aqueous suspensions of the products to be seeded, and whenthe deposit is dried, are infected with mildew conidia. After 12 daysthe results are read by counting the number of mildew infections on eachleaf.

In the following table is reported the average of two repetitions, with5 leaves per dose in each test.

In the following table is reported the aver-age of two repetitions with10 leaves per dose in each test.

Percent infection compared with that of the untreated control (averageinfection of the untreated control:

Test dose, about spots per leaf) percent 2 5 of a.s. l-chloro-Z-p-1-chloro-2- (2,4 1-chloro-2- (3-nitrophenyldinitrophenylnitro-4-chlorosulfonyl-ethylenesulfonyD-ethylene phenysulfonyl)- ethylene in which X is selected fromthe group consisting of H, Cl and N0 2. The method of claim 1, whereinthe compound is 1-chl0ro-2-p-nitrophenyl-sulfonyl-ethylene.

3. The method of claim 1, wherein the compound'isl-chloro-Z-(2,4-dinitrophenyl-sulfonyl)-ethylene.

'4. The method of claim 1, wherein the compound is1-chloro2-(3-nitro-4-chlorophenyl-sulfonyl)ethylene.

5. The method of claim 1, wherein the compound is l-chloro-23-nitrophenyl-sulfonyl)-ethylene.

Percent infection compared with that of the untreated control (averageinfection of untreated Test dosfie, control: about spots per leaf)percen of as. Zinc ethylene bis1-chloro-2-p-nitrol-chloro-2-(2,4-dinitrol-chloro-2-(3-nitro-4-dithiocarbamatephenyl-sulfonylethylphenylsulfonyD-ethylchlorophenylsulfonyD- ene eneethyle EXAMPLE '8 Activity test on Botrytis fabae Broad bean leaves,grown on sand unden artificial light, are removed and preserved on thebottom of Petri dishes, adapted to act as a wet room by means of afilter paper sheet kept wet by a small piece of synthetic spongeimpregnated with water.

References Cited UNITED STATES PATENTS 3,242,041 3/ 1966 Aichenegg eta1.

ALBERT T. MEY-ERS, Primary Examiner.

J. GOLDBERG, Assistant Examiner.

